Method for synthesizing cis-alpha-allyl-beta, gamma-unsaturated carboxylic acid ester

A technology of allyl acetate and allyl, which is applied in the direction of carboxylate preparation, chemical instruments and methods, organic chemistry methods, etc., can solve the problems such as insufficient synthesis methods, and achieve high regio and stereoselectivity, high Stereoselective, easy-to-operate effects

Inactive Publication Date: 2008-12-10
ZHEJIANG UNIV
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Problems solved by technology

[0003] The cis-alpha-allyl-beta of prior art report, the synthetic method of gamma-unsaturated carboxylate is not extensive enough, convenient

Method used

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  • Method for synthesizing cis-alpha-allyl-beta, gamma-unsaturated carboxylic acid ester
  • Method for synthesizing cis-alpha-allyl-beta, gamma-unsaturated carboxylic acid ester

Examples

Experimental program
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Effect test

Embodiment 1

[0021] Under nitrogen, ferric acetylacetonate (0.0072 g, 0.02 mmol), ethyl 2-methyl-4-phenyl-2,3-butadienoate (0.0805 g, 0.4 mmol) and Toluene (5 ml) was cooled to minus 78 degrees, and a solution of methylmagnesium chloride in tetrahydrofuran (0.4 ml, 3 equivalents, 1.2 mmol) was added dropwise to the system. After the addition was completed and reacted for 1 hour, tetrakis(triphenylphosphine) palladium (0.0225 g, 0.02 mmol) and allyl acetate (0.22 ml, d=0.928 g / ml, 0.2000 g, 2 mmol, 5 Equivalent) to react under stirring for 1. hour, naturally return to room temperature and react overnight, cool to zero and add dropwise saturated ammonium chloride solution to quench the reaction. Naturally warmed to room temperature, added water, extracted with ether, washed once with 1% hydrochloric acid, saturated sodium bicarbonate, and saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and flash column chromatography gave 2-allyl-2 , 0.0691 g of ethyl 3-dimethy...

Embodiment 2

[0024] According to the method described in Example 1, the difference is that the substrate and reagent used are: iron acetylacetonate (0.0073 grams, 0.02 mmol), 2-methyl-4-(4'-fluorophenyl)-2, Ethyl 3-butadienoate (0.0892 g, 0.4 mmol), tetrakis(triphenylphosphine) palladium (0.0230 g, 0.02 mmol) and allyl acetate (0.22 ml, d=0.928 g / ml, 0.2000 grams, 2 mmoles, 5 equivalents) to get 0.0817 grams of 2-allyl-2,3-dimethyl-4-(4'-fluorophenyl)-3(Z)-butenoic acid ethyl ester, product The rate is 74%. The product is a colorless liquid.

[0025] 1 H NMR (300MHz, CDCl 3 )δ7.10-7.01 (m, 2H), 6.98-6.88 (m, 2H), 6.41 (s, 1H), 5.75-5.58 (m, 1H), 5.08-4.95 (m, 2H), 3.66 (dq, J 1 =10.8Hz,J 2 =7.2Hz, 1H), 3.56(dq, J 1 =10.8Hz,J 2 =7.2Hz, 1H), 2.50-2.32(m, 2H), 1.91(d, J=1.2Hz, 3H), 1.27(s, 3H), 1.08(t, J=7.2Hz, 3H); 13 C NMR (CDCl 3 , 75MHz) δ175.2, 161.4 (d, J=244Hz), 139.7, 134.1 (d, J=3.1Hz), 133.9, 130.5 (d, J=7.9Hz), 126.8, 118.2, 114.4 (d, J= 21.8Hz), 60.3, 50.0, 42.8, 23.1, ...

Embodiment 3

[0027] According to the method described in Example 1, the difference is that the substrate and reagent used are: iron acetylacetonate (0.0070 g, 0.02 mmol), 2-methyl-4-(4'-chlorophenyl)-2, Ethyl 3-butadienoate (0.0959 g, 0.4 mmol), tetrakis(triphenylphosphine) palladium (0.0230 g, 0.02 mmol) and allyl acetate (0.22 ml, d=0.928 g / ml, 0.2000 grams, 2 mmoles, 5 equivalents) get 0.0770 grams of 2-allyl-2,3-dimethyl-4-(4'-chlorophenyl)-3(Z)-butenoic acid ethyl ester, produce The rate is 66%. The product is a colorless liquid.

[0028] 1 H NMR (300MHz, CDCl 3 )δ7.22(d, J=8.0Hz, 2H), 7.03(d, J=8.0Hz, 2H), 6.40(s, 1H), 5.75-5.58(m, 1H), 5.06-4.96(m, 2H ), 3.73-3.53(m, 2H), 2.50-2.30(m, 2H), 1.91(s, 3H), 1.26(s, 3H), 1.08(t, J=7.2Hz, 3H); 13 C NMR (CDCl 3 , 75MHz) δ175.1, 140.0, 136.7, 133.8, 132.2, 130.2, 127.7, 126.7, 118.3, 60.4, 50.1, 42.7, 23.1, 13.9; IR (neat, cm -1 ) 2979, 1730, 1640, 1593, 1488, 1230, 1091; MS (API-ES, m / z) 317.0 ((M( 37 Cl)+Na + ), 2.51), 315.1((M( ...

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Abstract

The invention relates to a cis-alpha-allyl-belta, gamma-unsaturated carboxylic ester and a method for synthesizing the same. The method comprises the following steps that: a1,4-addition of a Grignard reagent and an allenoic ester, is conducted to give a 1,3-conjugated diene magnesia salt at a temperature of below 78 DEG C under the catalytic action of ferric acetylacetonate. The 1,3-conjugated diene magnesia salt reacts with allyl acetates under the catalytic action of tetrakis(triphenylphosphine)platinum to give a series of cis-alpha-allyl-belta, gamma-unsaturated carboxylic ester compounds. The synthetic method has the advantages that the operation is simple, the raw materials and reagents are readily available, the reaction has high regional and vertical selectivity and can substitute two groups at the same time, the products can be separated and purified easily, and can be used to synthesize various cis-alpha-allyl-belta, gamma-unsaturated carboxylic esters.

Description

technical field [0001] The invention relates to a method for synthesizing cis-alpha-allyl-beta, gamma unsaturated carboxylic acid ester. Background technique [0002] Cis α-allyl-β, γ-unsaturated carboxylic acid ester is one of the most important intermediates in organic synthesis and one of the most common structural units in natural products. It has a variety of important physiological activities. In the field of biotechnology, medicine and pesticides have great development and utilization value. Since the double bond is at the β, γ position, the product tends to isomerize into a stable α, β-unsaturated structure, Iron-Catalyzed Highly Regio-and Stereoselective Conjugate Addition of 2, 3-Allenoates with Grignard Reagents, Zhan Lu, Guobi Chai, and Shengming Ma, J.Am.Chem.Soc.2007, 129, 14546-14547 reported that under iron catalysis, Grignard reagent and 2,3-alkenyl ester can undergo 1,4-addition reaction, using saturated Ammonium chloride quenching allows highly regio- an...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/333C07C69/618B01J31/24B01J31/28C07B37/00C07B49/00
Inventor 麻生明陆展柴国璧张小兵
Owner ZHEJIANG UNIV
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